N,n&#39;-diacetic acid-n&#39;-cyanomethyl, salts thereof, and their preparation

ABSTRACT

A novel intermediate useful in the synthesis of ethylenediaminetriacetic acid (ED3A) or its salts. A salt of N,N&#39;-ethylenediaminediacetic acid (ED2AH 2 ) is condensed with formaldehyde to form a stable 5-membered ring intermediate. The addition of cyanide across this cyclic material forms ethylenediamine N,N&#39;-diacetic acid-N&#39;-cyanomethyl or salts thereof (mononitrile-diacid), which is a useful intermediate in the production of ED3A. The nitrile in aqueous solutions may be spontaneously cyclized to form 2-oxo-1,4-piperazinediacetic acid (3KP) or salts thereof. In the presence of excess base, salts of ED3A are formed in excellent yield and purity.

This is a divisional of co-pending application, Ser. No. 07/806,032, filed Dec. 12, 1991 allowed:

BACKGROUND OF THE INVENTION

Ethylenediaminetriacetic acid (ED3A) or its salts (such as ED3ANa₃) has applications in the field of chelating chemistry, and may be used as a starting material in the preparation of strong chelating polymers, oil soluble chelants, surfactants and others. Conventional routes for the synthesis of ethylenediaminetriacetic acid were achieved via its N-benzyl derivative, which was subsequently hydrolyzed in alkaline solutions to ED3ANa₃, thus avoiding cyclization to its 2-oxo-1,4-piperazinediacetic acid (3KP) derivative. Syntheses attempted by both the alkaline condensation of chloroacetic acid with ethylenediamine, and the carboxymethylation of the diamine with formaldehyde and sodium cyanide resulted in complex mixtures requiring complex extraction techniques (e.g. almost exclusive solubility of 3KP in boiling dimethylformamide, Can. J. Chemistry 1970, 48(1), 163-175) to generate the desired product, and then in only relatively poor yield. In addition, conventional processes resulted in large quantities of by-product, such as ethylenediaminetetraacetic acid (ED4A). Where the by-products were especially objectionable, complicated blocking techniques were necessary in order to achieve a relatively pure solution.

One example of the synthesis of ethylenediamine-N,N,N'-triacetic acid is shown in Chemical Abstracts 78, Vol. 71, page 451, no. 18369c, 1969. There it is disclosed that ethylenediamine reacts with ClH₂ CCO₂ H in a 1:3 molar ratio in basic solution at 10° C. for 24 hours to form a mixture from which ethylenediamine-N,N,N'-triacetic acid can be separated by complexing the same with Co(III). The resulting cobalt complexes can be isolated through ion exchange.

The instant invention is directed to a novel composition of matter that is useful as an intermediate in the synthesis of ethylenediaminetriacetic acid or its salts in high conversions and excellent yield.

SUMMARY OF THE INVENTION

The problems of the prior art have been overcome by the instant invention, which provides a novel composition of matter useful as an intermediate in the synthesis of ethylenediaminetriacetic acid. Specifically, a mononitrile-diacid is formed by reacting a salt of N,N'-ethylenediaminediacetic acid (ED2AH₂) with formaldehyde to form a stable 5-membered ring intermediate. The addition of cyanide across this cyclic material forms ethylenediamine N,N'-diacetic acid-N'-cyanomethyl or salts thereof (the mononitrile-diacid). This nitrile in aqueous solutions may be spontaneously cyclized to form 3KP or salts thereof, which in the presence of excess base, forms salts of ED3A in excellent yield and purity.

DETAILED DESCRIPTION OF THE INVENTION

Suitable salts of ethylenediaminediacetic acid useful as the starting material in the instant invention include alkali and alkaline earth metal salts, in particular, the sodium and potassium salts. For purposes of illustration, the sodium salt will be used, although it should be understood that other salts may be employed without departing from the spirit and scope of the invention. One suitable reaction scheme for the synthesis of the mononitrile-diacid is the alkaline condensation of formaldehyde with N,N'-ethylenediamine disodium acetate to form a 5-membered ring structure, 1,3-bis(carboxymethyl)imidazolidine, and is illustrated as follows: ##STR1##

The above reaction may be carried out in the presence of additional base. Suitable bases include alkali and alkaline earth metal hydroxides, preferably sodium and potassium hydroxide. Compound (I) is the bridged reaction product of EDDANa.sub.(1.0→2.0) and formaldehyde, which the present inventor has found to be a stable intermediate in the ED3A synthesis. Compound (I) is formed easily between 0° and 110° C. The reaction proceeds quickly and forms readily at pH's greater than about 7.0. Preferably the temperature employed is about 0° to 65° C., most preferably 15° to 65° C., although temperatures higher than 65° C. are operable. Formaldehyde can be used in stoichiometric amounts, although it is preferred that a slight molar excess be used, preferably 0.5%-0.2%. Preferably the concentration of the formaldehyde is 55% or less in aqueous solution. Paraformaldehyde also can be used.

The second step in the reaction scheme is illustrated below: ##STR2##

Compound (II) is readily formed at temperatures between 0° and 110° C. The reaction should be conducted at temperatures at or below the boiling point of the solution. Preferably the reaction is carried out at temperatures from about 0° to about 65° C., most preferably about 15° to 65° C. to enhance the reaction rate. Suitable sources of cyanide include gaseous hydrogen cyanide, an aqueous solution of hydrogen cyanide, or alkali metal cyanide such as sodium cyanide or potassium cyanide, etc. The cyanide may be used in stoichiometric amounts, although slight molar excesses may be used, preferably 0.5%-2.0%.

Compound (II) is useful as an intermediate for the production of ED3A. Specifically, compound (II) may be hydrolyzed to the monoamide-diacid compound (III) (partially hydrolyzed mononitrile diacid), which spontaneously cyclizes to 3KP. Compound (IV) forms readily in the presence of a base such as alkali metal or alkaline earth metal hydroxides. Preferably the base is NaOH. Mole ratios of <3.0M base:1M ED2AH₂ but preferably <2.0M base:1M ED2AH₂ are employed. Higher concentrations of base (i.e. >3.0M base: M ED2AH₂) cause some disproportionation of the diacid mononitrile and some ED4A (ethylenediaminetetraacetic acid) is formed, especially at temperatures >65° C. In particular, the concentration of ED4A is found to be in direct proportion to the amount of excess caustic employed, when high temperature reactions are conducted and high molar ratios of base are employed (>2.0M base: 1M ED2AH₂), which may be attributed to the simultaneous hydrolysis of 3KP and disproportionation of the mononitrile-diacid. When the mole ratio of base to ED2A is <2.0, higher temperatures may be used. Also, in Step III ammonia is eliminated between an amide group and an imino group on the same molecule. However, at lower temperatures (<65° C.) higher amounts of base may be employed (>2.0M) and hydrolysis of compound (II) can proceed directly to ED3A without cyclization. ##STR3##

The 3KPNa₂ is then hydrolyzed by at least the addition of 1 equivalent of caustic, preferably a 1 molar excess of caustic. This amounts to approximately 5% weight excess (free) caustic in solution on a 40% ED3ANa₃ solution. The solution is boiled under atmospheric pressure to the desired concentration. Preferably the reaction is carried out by raising the temperature from the temperature in the formation of compound (IV) reaction to the boil over a period from about 30 minutes to about 6 hours. ##STR4##

The resulting solutions typically give approximately 35-40% ED3ANa₃, with approximately 2% 3KPNa₂ remaining as an unopened ringed structure. This corresponds to about a 94% conversion to ED3ANa₃, with the remaining 6% of mass existing as 3KPNa₂. Acidification of this mass to pH's <6.0 to produce ED3AH₃ is not possible, as cyclization to 3KPH₂ will eventually occur.

The foregoing synthetic scheme results in conversions to ED3ANa₃ in excess of 90%, with the residual proportion being 3KPNa₂ to give a total mass balance of virtually 100%. The reactions are tolerant to a wide pH range.

The following procedure to obtain ED2AH₂ was for experimental purposes only. Far less elaborate schemes for the production of ED2AH₂ are possible. Any schemes known in the art can be employed for the production of ED2AH₂ and its salts, and the instant invention is not to be limited by any particular scheme.

In the following examples, all batches were synthesized from EDDAH₂ (98.20%) obtained by acidification of EDDANa₂ to a pH of 5.50 with nitric acid, while maintaining the temperature of the solution <10° C. The resultant slurry was filtered by means of a Buchner funnel with the vacuum provided by a water aspirator. The filter cake was washed with approximately 7 liters of iced H₂ O. To enhance drying, the cake was then washed with approximately 1 liter of MeOH. The crystals were then placed on 1 inch deep stainless steel trays, dried in a Stokes vacuum dryer, model 338F at 40° C. under a vacuum of 4 mm Hg, for 12 hours. Approximately 2 Kg of a white crystalline powder was recovered. Analysis of this powder showed it to be 98.2% ED2AH₂.

All batches were synthesized on a 0.5 liter scale. 88 g of ED2AH₂ were charged to a 500 ml conical flask and diluted with 180 mls of H₂ O. 50% caustic was used to obtain the sodium salt in the ratio required. The solution was stirred for 30 minutes, and then charged to a 1 liter 5-necked round bottom flask. The conical flask was then washed with 20 mls. of H₂ O, and the washings transferred to the round bottom flask. The round bottom flask was equipped with a magnetic stirring bar, a condenser (ethylene glycol/H₂ O @ 0° C.), A 0-250° C. mercury thermometer, and a J-type thermocouple that provided a signal to a Love proportional controller, which maintained the temperature at the desired level were employed. A Glass-Col heating mantle controlled by the Love controller via a Powerstat variable autotransformer was used to heat the contents of the flask. 37% CH₂ O and 100% HCN were pumped at approximately 1 g/minute and 0.50 g/minute, respectively, by an FMI micro metering pump at a setting of 0.5, via 1/8" Teflon tubing to the flask. A 125 ml addition funnel equipped with a Teflon metering valve, and a condenser with the same coolant as described above, was used as the reservoir for the reactants to be pumped. Table 1 shows the results for the experiments conducted up to the spontaneous cyclization of monoamide-diacid after it has been hydrolyzed. The mononitrile-diacid was not isolated; however, it was identified by HPLC as being the precursor to 3KP. 3KP was more easily quantified by HPLC, and it is that compound which is quantitatively shown in Table 1. Table 2 shows results for ED3A produced for 9 conditions using the compound of the instant invention.

                                      TABLE 1                                      __________________________________________________________________________                                                      %                                                                              EDDA                                                    Moles                                                                              lc %  lc      lc % to  % Unrxl                                                                             Mass                 Exp Tot wt                                                                             Comments  temp                                                                               l(mins)                                                                            EDDA                                                                               EDDANa2                                                                              % ED3ANa3                                                                              3KPNa2                                                                              Produc                                                                             EDDA balance              __________________________________________________________________________                                   220.00                                                                               300.00  260.00                             1 - 0                                                                              240.75                                                                             2NaH/1EDDA                                                                               50  0.0 0.247                                                                              22.57%                                                                               0.00%   0.00%                                                                               0.00%                                                                              100.00%                                                                             100.00%              1 - 1                                                                              238.98                                                                             50° C.                                                                            50  55.0                                                                               0.245                                                                              4.36% 0.30%   11.68%                                                                              44.76%                                                                             19.32%                                                                              64.00%               1 - 2                                                                              234.04        50  102.0                                                                              0.240                                                                              3.03% 0.50%   15.15%                                                                              50.42%                                                                             13.42%                                                                              71.84%               1 - 3                                                                              228.13        50  144.0                                                                              0.234                                                                              2.13% 0.60%   17.50%                                                                              67.55%                                                                             9.44%                                                                               76.99%               1 - 4                                                                              221.69        50  199.0                                                                              0.227                                                                              1.51%         19.21%                                                                              72.02%                                                                             6.69%                                                                               78.71%               1 - 5                                                                              214.52        50  250.0                                                                              0.220                                                                              1.14%         20.54%                                                                              77.00%                                                                             5.05%                                                                               82.05%               1 - 6                                                                              208.17        50  300.0                                                                              0.214                                                                              0.89% 1.20%   20.90%                                                                              82.25%                                                                             3.94%                                                                               86.19%               final                                                                              202.88                                                                     sc                                                                             2 - 0                                                                              240.75                                                                             2NaH/1EDDA                                                                               65  0.0 0.247                                                                              22.57%        0.00%                                                                               0.00%                                                                              100.00%                                                                             100.00%              2 - 1                                                                              240.75                                                                             65° C.                                                                            65  15.0                                                                               0.247                                                                              3.84%         13.94%                                                                              52.26%                                                                             17.01%                                                                              69.27%               2 - 2                                                                              236.21        65  45.0                                                                               0.242                                                                              258%          17.68%                                                                              66.28%                                                                             11.43%                                                                              77.71%               2 - 3                                                                              231.19        65  90.0                                                                               0.237                                                                              1.49%         20.89%                                                                              78.31%                                                                             6.60%                                                                               84.91%               2 - 4                                                                              226.19        65  135.0                                                                              0.232                                                                              1.45%         21.64%                                                                              81.12%                                                                             6.42%                                                                               87.55%               2 - 5                                                                              220.81        65  186.0                                                                              0.227                                                                              1.41%         21.81%                                                                              81.76%                                                                             6.25%                                                                               88.01%               2 - 6                                                                              214.61        65  230.0                                                                              0.220                                                                              1.36%         21.73%                                                                              81.46%                                                                             6.03%                                                                               87.49%               2 - 7                                                                              210.35        65  262.0                                                                              0.216                                                                              1.28%         21.74%                                                                              81.50%                                                                             5.67%                                                                               87.17%               2 - 8                                                                              205.34        65  990.0                                                                              0.211                                                                              1.23%         21.60%                                                                              80.97%                                                                             5.45%                                                                               86.42%               final                                                                              197.00                                                                     sc                                                                             3 - 0                                                                              240.75                                                                             2NaH/1EDDA                                                                               80  0.0 0.247                                                                              22.57%        0.00%                                                                               0.00%                                                                              100.00%                                                                             100.00%              3 - 1                                                                              239.86                                                                             80° C.                                                                            80  10.0                                                                               0.246                                                                              4.16%         15.92%                                                                              59.68%                                                                             18.43%                                                                              78.11%               3 - 2                                                                              235.19        80  35.0                                                                               0.241                                                                              3.66%         18.66%                                                                              69.95%                                                                             16.22%                                                                              86.17%               3 - 3                                                                              229.91        80  75.0                                                                               0.236                                                                              3.33%         19.61%                                                                              73.51%                                                                             14.75%                                                                              88.27%               3 - 4                                                                              223.28        80  136.0                                                                              0.229                                                                              3.04%         19.50%                                                                              73.10%                                                                             13.47%                                                                              86.57%               3 - 5                                                                              217.66        80  210.0                                                                              0.223                                                                              2.89%         19.77%                                                                              74.11%                                                                             12.80%                                                                              86.92%               3 - 6                                                                              211.34        80  280.0                                                                              0.217                                                                              2.69%         199.99%                                                                             74.94%                                                                             11.92%                                                                              86.86%               final                                                                              205.07                                                                     sc                                                                             4 - 0                                                                              239.10                                                                             1.9NaH/1EDDA                                                                             50  0.0 0.247                                                                              22.73%        0.00%                                                                               0.00%                                                                              100.00%                                                                             100.00%              4 - 1                                                                              239.10                                                                             50° C.                                                                            50  30.0                                                                               0.247                                                                              6.73%         6.34%                                                                               23.60%                                                                             29.61%                                                                              53.22%               4 - 2                                                                              234.00                                                                             1.0 CH2O  50  70.0                                                                               0.242                                                                              5.00%         10.24%                                                                              38.12%                                                                             22.00%                                                                              60.13%               4 - 3                                                                              228.81        50  115.0                                                                              0.236                                                                              4.18%         13.58%                                                                              50.56%                                                                             18.39%                                                                              58.95%               4 - 4                                                                              223.25        50  165.0                                                                              0.231                                                                              2.68%         16.40%                                                                              61.06%                                                                             11.79%                                                                              72.85%               4 - 5                                                                              217.35        50  200.0                                                                              0.225                                                                              2.16%         17.99%                                                                              66.98%                                                                             9.50%                                                                               76.48%               4 - 6                                                                              212.72        50  250.0                                                                              0.220                                                                              1.52%         19.66%                                                                              73.20%                                                                             6.69%                                                                               79.89%               4 - 7                                                                              208.46        50  285.0                                                                              0.215                                                                              1.14%         20.75%                                                                              77.26%                                                                             5.02%                                                                               82.27%               4 - 8                                                                              192.50        50  1280.0                                                                             0.199                                                                              0.13% 1.10%   23.50%                                                                              91.04%                                                                             0.57%                                                                               91.62%               final                                                                              138.00        boiled  0.201                                                                              0.13%         32.75%                                                                              86.36%                                                                             0.41%                                                                               86.77%               so                                                                             5 - 0                                                                              241.10                                                                             2.1NaH/1EDDA                                                                             50  0   0.247                                                                              22.54%                                                                               0.00%   0.00%                                                                               0.00%                                                                              100.00%                                                                             100.00%              5 - 1                                                                              241.10                                                                             50° C.                                                                            50  40.0                                                                               0.247                                                                              5.58% 0.10%   9.35%                                                                               35.43%                                                                             24.76%                                                                              60.19%               5 - 2                                                                              236.01                                                                             1.05 CH2O 50  90.0                                                                               0.242                                                                              3.85% 0.20%   14.31%                                                                              54.37%                                                                             17.08%                                                                              71.46%               5 - 3                                                                              231.32        50  130.0                                                                              0.237                                                                              2.75% 0.50%   17.20%                                                                              66.20%                                                                             12.20%                                                                              78.40%               5 - 4                                                                              225.41        50  186.0                                                                              0.231                                                                              2.15% 0.80%   18.60%                                                                              72.43%                                                                             9.54%                                                                               81.97%               5 - 5                                                                              220.92        50  228.0                                                                              0.226                                                                              1.71% 1.00%   19.41%                                                                              76.12%                                                                             7.59%                                                                               83.71%               5 - 6                                                                              216.39        50  260.0                                                                              0.222                                                                              1.49% 1.30%   19.85%                                                                              78.75%                                                                             6.61%                                                                               85.36%               5 - 7                                                                              211.83        50  1350.0                                                                             0.217                                                                              0.66% 3.40%   16.01%                                                                              71.17%                                                                             2.93%                                                                               74.10%               final                                                                              170.21        boiled  0.220                                                                              0.92% 5.10%   23.10%                                                                              82.02%                                                                             3.24%                                                                               85.26%               so                                                                             5 - 0                                                                              239.10                                                                             1.9NaH/1EDDA                                                                             80  0.0 0.247                                                                              22.73%        0.00%                                                                               0.00%                                                                              100.00%                                                                             100.00%              5 - 1                                                                              239.10                                                                             80° C.                                                                            80  15.0                                                                               0.247                                                                              3.61%         17.05%                                                                              63.48%                                                                             15.80%                                                                              79.36%               5 - 2                                                                              233.80                                                                             1.05 CH2O 80  45.0                                                                               0.242                                                                              2.01%         18.70%                                                                              69.62%                                                                             13.24%                                                                              82.87%               5 - 3                                                                              229.09        80  90.0                                                                               0.237                                                                              2.61%         19.78%                                                                              73.64%                                                                             11.48%                                                                              85.13%               5 - 4                                                                              222.74        80  145.0                                                                              0.230                                                                              2.26%         20.36%                                                                              75.80%                                                                             9.04%                                                                               85.75%               5 - 5                                                                              271.86        80  189.0                                                                              0.225                                                                              1.32%         20.11%                                                                              74.87%                                                                             5.81%                                                                               80.68%               5 - 6                                                                              213.47        80  240.0                                                                              0.221                                                                              1.60%         18.26%                                                                              67.98%                                                                             7.04%                                                                               75.02%               5 - 7                                                                              208.33        80  285.0                                                                              0.215                                                                              1.66%         21.35%                                                                              79.49%                                                                             7.30%                                                                               86.79%               5 - 8                                                                              203.47        80  1282.0                                                                             0.210                                                                              0.40% 0.10%   20.90%                                                                              78.14%                                                                             1.76%                                                                               79.90%               5 - 9                                                                              157.60        boiled  0.213                                                                              0.60% 0.50%   27.75%                                                                              80.30%                                                                             2.02%                                                                               82.32%               6 - 0                                                                              241.10                                                                             2.1NaH/1EDDA                                                                             80  0.0 0.247                                                                              22.54%                                                                               0.00%   0.00%                                                                               0.00%                                                                              100.00%                                                                             100.00%              6 - 1                                                                              241.10                                                                             80° C.                                                                            80  20.0                                                                               0.247                                                                              3.72% 1.00%   18.17%                                                                              71.47%                                                                             16.51%                                                                              87.97%               6 - 2                                                                              234.20                                                                             1.00 CH2O 80  74.0                                                                               0.241                                                                              3.44% 1.00%   19.09%                                                                              74.92%                                                                             15.26%                                                                              90.19%               6 - 3                                                                              229.95        80  110.0                                                                              0.236                                                                              3.47% 1.00%   19.15%                                                                              75.15%                                                                             15.40%                                                                              90.54%               6 - 4                                                                              225.49        80  155.0                                                                              0.231                                                                              3.37% 1.00%   19.44%                                                                              76.24%                                                                             14.95%                                                                              91.19%               6 - 5                                                                              220.51        80  200.0                                                                              0.226                                                                              3.14% 1.00%   19.06%                                                                              74.81%                                                                             13.93%                                                                              88.74%               6 - 6                                                                              215.06        80  238.0                                                                              0.220                                                                              3.15% 1.00%   19.20%                                                                              75.34%                                                                             13.98%                                                                              89.31%               6 - 7                                                                              210.36        80  286.0                                                                              0.216                                                                              3.06% 1.00%   18.81%                                                                              73.87%                                                                             13.58%                                                                              87.45%               6 - 8                                                                              204.01        80  320.0                                                                              0.209                                                                              3.08% 1.00%   19.19%                                                                              75.30%                                                                             13.67%                                                                              88.96%               6 - 9                                                                              198.58        80  1286.0                                                                             0.203                                                                              2.30% 1.70%   19.39%                                                                              78.33%                                                                             10.20%                                                                              88.53%               6 - 10                                                                             145.33        boiled  0.206                                                                              2.49% 1.80%   21.94%                                                                              63.79%                                                                             7.99%                                                                               71.78%               7 - 0                                                                              239.10                                                                             1.9NaH/1EDDA                                                                             80  0.0 0.247                                                                              22.73%        0.00%                                                                               0.00%                                                                              100.00%                                                                             100.00%              7 - 1                                                                              239.10                                                                             80° C.                                                                            80  26.0                                                                               0.247                                                                              3.32%         16.83%                                                                              62.66%                                                                             14.61%                                                                              77.27%               7 - 2                                                                              233.84                                                                             1.00 CH2O 80  71.0                                                                               0.242                                                                              2.87%         19.69%                                                                              73.31%                                                                             12.63%                                                                              85.94%               7 - 3                                                                              228.66        80  119.0                                                                              0.236                                                                              2.42%         19.79%                                                                              73.68%                                                                             10.65%                                                                              84.33%               7 - 4                                                                              223.62        80  160.0                                                                              0.231                                                                              2.31%         20.21%                                                                              75.24%                                                                             10.16%                                                                              85.41%               7 - 5                                                                              218.59        80  208.0                                                                              0.226                                                                              1.99%         20.36%                                                                              75.80%                                                                             8.76%                                                                               84.56%               7 - 6                                                                              213.40        80  260.0                                                                              0.220                                                                              1.88%         20.24%                                                                              75.36%                                                                             8.27%                                                                               83.63%               7 - 7                                                                              207.57        80  1291.0                                                                             0.214                                                                              0.51%         19.05%                                                                              73.90%                                                                             2.24%                                                                               76.15%               7 - 8                                                                              127.47        boiled  0.217                                                                              0.94% 1.80%   30.58%                                                                              72.60%                                                                             2.51%                                                                               75.11%               8 - 0                                                                              239.10                                                                             1.9NaH/1EDDA                                                                             50  0.0 0.247                                                                              22.73%        0.00%                                                                               0.00%                                                                              100.00%                                                                             100.00%              8 - 1                                                                              239.10                                                                             50° C.                                                                            50  35.0                                                                               0.247                                                                              1.89%         20.44%                                                                              76.10%                                                                             8.32%                                                                               84.42%               8 - 2                                                                              233.30                                                                             1.05 CH2O 50  117.0                                                                              0.241                                                                              1.29%         22.46%                                                                              83.62%                                                                             5.60%                                                                               89.30%               8 - 3                                                                              228.81        50  160.0                                                                              0.236                                                                              1.07%         23.18%                                                                              86.30%                                                                             4.71%                                                                               91.01%               8 - 4                                                                              223.96        50  210.0                                                                              0.231                                                                              0.82%         23.29%                                                                              86.71%                                                                             3.61%                                                                               90.32%               8 - 5                                                                              218.87        50  297.0                                                                              0.226                                                                              0.56%         24.16%                                                                              89.95%                                                                             2.46%                                                                               92.42%               8 - 6                                                                              199.40        50  1261.0                                                                             0.206                                                                              0.24%         24.96%                                                                              92.93%                                                                             1.06%                                                                               93.99%               8 - 7                                                                              141.00        boiled  0.206                                                                              0.27% 1.10%   35.02%                                                                              94.71%                                                                             0.84%                                                                               95.55%               9 - 0                                                                              241.10                                                                             2.1NaH/1EDDA                                                                             50  0.0 0.247                                                                              22.54%        0.00%                                                                               0.00%                                                                              100.00%                                                                             100.00%              9 - 1                                                                              241.10                                                                             50° C.                                                                            50  30.0                                                                               0.247             9.07%                                                                               34.05%                                                                             0.00%                                                                               34.05%               9 - 2                                                                              235.44                                                                             1.00 CH2O 50  112.0                                                                              0.241                                                                              2.71% 0.60%   16.04%                                                                              62.17%                                                                             12.02%                                                                              74.19%               9 - 3                                                                              230.22        50  168.0                                                                              0.236                                                                              2.10% 0.70%   18.36%                                                                              71.21%                                                                             9.32%                                                                               80.52%               9 - 4                                                                              225.60        50  211.0                                                                              0.231                                                                              1.55% 1.10%   19.28%                                                                              75.96%                                                                             6.88%                                                                               82.84%               9 - 5                                                                              220.60        50  250.0                                                                              0.226                                                                              1.02% 1.20%   20.77%                                                                              81.88%                                                                             4.53%                                                                               86.41%               9 - 6                                                                              214.87        50  1380.0                                                                             0.220                                                                              0.89% 3.30%   20.16%                                                                              86.42%                                                                             3.95%                                                                               90.37%               9 - 7                                                                              112.00        boiled  0.223                                                                              1.51% 9.60%   34.28%                                                                              82.36%                                                                             3.45%                                                                               85.81%               10 - 0                                                                             241.10                                                                             2.1NaH/1EDDA                                                                             80  0.0 0.247                                                                              22.54%                                                                               0       0.00%                                                                               0.00%                                                                              100.00%                                                                             100.00%              10 - 1                                                                             241.10                                                                             80° C.                                                                            80  30.0                                                                               0.247                                                                              3.82% 0.70%   19.28%                                                                              74.66%                                                                             16.95%                                                                              91.61%               10 - 2                                                                             236.36                                                                             1.05 CH2O 80  88.0                                                                               0.242                                                                              3.42% 0.60%   19.50%                                                                              75.16%                                                                             15.17%                                                                              90.33%               10 - 3                                                                             231.84        80  133.0                                                                              0.238                                                                              3.32% 0.80%   20.04%                                                                              77.84%                                                                             14.73%                                                                              92.57%               10 - 4                                                                             226.84        80  196.0                                                                              0.232                                                                              2.99% 0.50%   17.77%                                                                              68.34%                                                                             13.27%                                                                              81.61%               10 - 5                                                                             221.45        80  240.0                                                                              0.227                                                                              3.21% 0.70%   20.42%                                                                              78.94%                                                                             14.24%                                                                              93.18%               10 - 6                                                                             216.41        80  293.0                                                                              0.222                                                                              3.09% 0.01%   19.99%                                                                              75.07%                                                                             13.71%                                                                              88.78%               10 - 7                                                                             210.56        80  1290.0                                                                             0.216                                                                              2.16% 1.00%   19.30%                                                                              75.71%                                                                             9.58%                                                                               85.30%               10 - 8                                                                             138.64        boiled  0.218                                                                              3.22% 2.50%   28.68%                                                                              75.34%                                                                             9.29%                                                                               84.63%               11 - 0                                                                             263.10                                                                             3.1NaH/1EDDA                                                                             35  0.0 0.247                                                                              20.65%                                                                               0.00%   0    0.00%                                                                              100.00%                                                                             100.00%              11 - 1                                                                             263.10                                                                             35° C.                                                                            35  35.0                                                                               0.247                                                                              8.47%         2.37%                                                                               9.71%                                                                              41.01%                                                                              50.72%               11 - 2                                                                             258.10                                                                             1.00 CH2O 35  72.0                                                                               0.242             4.89%                                                                               20.03%                                                                             0.00%                                                                               20.03%               11 - 3                                                                             252.90        35  143.0                                                                              0.237                                                                              7.21%         6.40%                                                                               26.22%                                                                             34.91%                                                                              61.13%               11 - 4                                                                             247.40        35  182.0                                                                              0.232                                                                              7.20% 0.60%   6.81%                                                                               30.03%                                                                             34.86%                                                                              64.89%               11 - 5                                                                             242.74        35  221.0                                                                              0.228                                                                              6.89% 0.70%   8.25%                                                                               36.28%                                                                             33.86%                                                                              69.64%               11 - 6                                                                             238.43        35  257.0                                                                              0.224                                                                              6.60% 1.10%   9.49%                                                                               42.78%                                                                             31.96%                                                                              74.74%               11 - 7                                                                             233.63        35  1360.0                                                                             0.219                                                                              2.88% 12.00%  9.08%                                                                               79.81%                                                                             13.94%                                                                              93.75%               11 - 8                                                                             140.00        boiled  0.222                                                                              4.22% 34.30%  5.27%                                                                               84.89%                                                                             12.10%                                                                              96.98%               12 - 0                                                                             263.10                                                                             3.1NaH/1EDDA                                                                             50  0.0 0.247                                                                              20.65%                                                                               0.00%   0.00%                                                                               0.00%                                                                              100.00%                                                                             100.00%              12 - 1                                                                             263.10                                                                             50° C.                                                                            50  13.0                                                                               0.247                                                                              6.20% 0.40%   12.39%                                                                              52.18%                                                                             30.02%                                                                              82.20%               12 - 2                                                                             257.27                                                                             1.00 CH2O 50  54.0                                                                               0.242                                                                              6.04% 1.80%   11.35%                                                                              52.09%                                                                             29.24%                                                                              82.13%               12 - 3                                                                             251.81        50  90.0                                                                               0.236                                                                              4.84% 3.50%   12.49%                                                                              63.60%                                                                             23.43%                                                                              87.03%               12 - 4                                                                             247.54        50  147.0                                                                              0.232                                                                              4.22% 4.90%   12.90%                                                                              70.25%                                                                             20.43%                                                                              90.68%               12 - 5                                                                             243.10        50  1237.0                                                                             0.228                                                                              3.47% 15.90%  8.07%                                                                               89.52%                                                                             16.80%                                                                              106.32%              12 - 6                                                                             138.80        boiled  0.231                                                                              5.50% 40.00%  5.45%                                                                               92.71%                                                                             15.02%                                                                              107.73%              13 - 0                                                                             271.10                                                                             3.5NaH/1EDDA                                                                             35  0.0 0.247                                                                              20.04%                                                                               0.00%   0    0.00%                                                                              100.00%                                                                             100.00%              13 - 1                                                                             271.10                                                                             35° C.                                                                            35  10.0                                                                               0.247                                                                              9.60%         4.02%                                                                               16.97%                                                                             47.89%                                                                              64.86%               13 - 2                                                                             265.99                                                                             1.00 CH2O 35  47.0                                                                               0.242                                                                              7.82%         8.07%                                                                               34.07%                                                                             39.01%                                                                              73.08%               13 - 3                                                                             261.37        35  90.0                                                                               0.238                                                                              7.31%         9.19%                                                                               38.79%                                                                             36.47%                                                                              75.26%               13 - 4                                                                             256.60        35  130.0                                                                              0.234                                                                              6.70% 0.80%   9.46%                                                                               42.86%                                                                             33.43%                                                                              76.29%               13 - 5                                                                             252.16        35  186.0                                                                              0.230                                                                              6.35% 0.80%   10.36%                                                                              46.66%                                                                             31.68%                                                                              78.34%               13 - 6                                                                             246.06        35  230.0                                                                              0.224                                                                              6.12% 1.40%   10.54%                                                                              49.62%                                                                             30.53%                                                                              80.15%               13 - 7                                                                             241.06        35  308.0                                                                              0.220                                                                              6.16% 2.30%   10.43%                                                                              52.44%                                                                             30.73%                                                                              83.18%               13 - 8                                                                             235.25        35  1320.0                                                                             0.214                                                                              2.52% 13.90%  6.98%                                                                               80.32%                                                                             12.57%                                                                              92.89%               burned                                                                         14 - 0                                                                             443.96                                                                             1.8NaH/1EDDA                                                                             65  13.0                                                                               0.491             5.30%                                                                               18.71%                                                                             0.00%                                                                               18.71%               14 - 1                                                                             442.63                                                                             65° C.                                                                            65  49.0                                                                               0.490             10.48%                                                                              36.45%                                                                             0.00%                                                                               36.45%               14 - 2                                                                             440.98                                                                             1.00 CH2O 65  107.0                                                                              0.488             16.17%                                                                              56.23%                                                                             0.00%                                                                               56.23%               14 - 3                                                                             439.19        65  1063.0                                                                             0.486             21.12%                                                                              73.45%                                                                             0.00%                                                                               73.45%               15 - 0                                                                             448.81                                                                             1.9NaH/1EDDA                                                                             50  25.0                                                                               0.491             2.05%                                                                               7.21%                                                                              0.00%                                                                               7.21%                15 - 1                                                                             447.52                                                                             50° C.                                                                            50  85.0                                                                               0.490             7.06%                                                                               24.82%                                                                             0.00%                                                                               24.82%               15 - 2                                                                             446.05                                                                             1.05 CH2O 50  122.0                                                                              0.488             9.97%                                                                               35.05%                                                                             0.00%                                                                               35.05%               15 - 3                                                                             444.25        50  173.0                                                                              0.486             13.01%                                                                              45.74%                                                                             0.00%                                                                               45.74%               15 - 4                                                                             443.14        50  1238.0                                                                             0.485             25.10%                                                                              88.25%                                                                             0.00%                                                                               88.25%               15 - 5                                                                             441.95        50      0.45              25.52%                                                                              89.48%                                                                             0.00%                                                                               89.48%               16 - 0                                                                             450.68                                                                             1.9NaH/1EDDA                                                                             65  10.0                                                                               0.491             6.67%                                                                               23.55%                                                                             0.00%                                                                               23.55%               16 - 1                                                                             449.03                                                                             65° C.                                                                            65  41.0                                                                               0.489             12.47%                                                                              44.02%                                                                             0.00%                                                                               44.02%               16 - 2                                                                             447.46                                                                             1.00 CH2O 65  82.0                                                                               0.487             17.76%                                                                              62.70%                                                                             0.00%                                                                               62.70%               16 - 3                                                                             446.18        65  125.0                                                                              0.486             20.24%                                                                              71.45%                                                                             0.00%                                                                               71.45%               16 - 4                                                                             444.85        65  1080.0                                                                             0.486             24.22%                                                                              85.25%                                                                             0.00%                                                                               85.25%               17 - 0                                                                             450.70                                                                             1.9NaH/1EDDA                                                                             75  17.0                                                                               0.491             14.87%                                                                              52.50%                                                                             0.00%                                                                               52.50%               17 - 1                                                                             449.45                                                                             75° C.                                                                            75  48.0                                                                               0.490             20.66%                                                                              72.94%                                                                             0.00%                                                                               72.94%               17 - 2                                                                             448.35                                                                             1.05 CH2O 75  98.0                                                                               0.488             24.26%                                                                              85.65%                                                                             0.00%                                                                               85.65%               17 - 3                                                                             447.08                                                                             75        75  239.0                                                                              0.487             24.97%                                                                              88.16%                                                                             0.00%                                                                               88.16%               17 - 4                                                                             445.66        75  1233.0                                                                             0.486             26.24%                                                                              92.64%                                                                             0.00%                                                                               92.64%               17 - 5                                                                             407.20        boil                                                                               boil                                                                               0.486             26.41%                                                                              85.19%                                                                             0.00%                                                                               85.19%               18 - 0                                                                             450.70                                                                             1.9NaH/1EDDA                                                                             50° C.                                                                      10.0                                                                               0.491             1.36%                                                                               4.80%                                                                              0.00%                                                                               4.80%                18 - 1                                                                             449.36                                                                             50° C.                                                                            50° C.                                                                      88.0                                                                               0.490             7.60%                                                                               26.83%                                                                             0.00%                                                                               26.83%               18 - 2                                                                             447.82                                                                             1.00 CH2O 50°  C.                                                                     1365.0                                                                             0.488             24.34%                                                                              85.93%                                                                             0.00%                                                                               85.93%               18 - 3                                                                             392.30        boil                                                                               boil                                                                               0.488             27.84%                                                                              86.10%                                                                             0.00%                                                                               86.10%               19 - 0                                                                             446.70                                                                             1.8NaH/1EDDA                                                                             50° C.                                                                      41.0                                                                               0.491             2.59%                                                                               9.06%                                                                              0.00%                                                                               9.06%                19 - 1                                                                             445.33                                                                             50° C.                                                                            50° C.                                                                      120.0                                                                              0.489             8.63%                                                                               30.20%                                                                             0.00%                                                                               30.20%               19 - 2                                                                             443.88                                                                             1.00 CH2O 50° C.                                                                      164.0                                                                              0.488             11.36%                                                                              39.75%                                                                             0.00%                                                                               39.75%               19 - 3                                                                             442.48        50° C.                                                                      1400.0                                                                             0.486             24.71%                                                                              85.46%                                                                             0.00%                                                                               85.46%               19 - 4                                                                             343.20        boil                                                                               boil                                                                               0.486             31.79%                                                                              86.28%                                                                             0.00%                                                                               86.28%               20 - 0                                                                             446.07                                                                             1.0NaH/1EDDA                                                                             60° C.                                                                      60.0                                                                               0.491             3.35%                                                                               11.71%                                                                             0.00%                                                                               11.71%               20 - 1                                                                             444.76                                                                             50° C.                                                                            50° C.                                                                      210.0                                                                              0.490             13.30%                                                                              46.47%                                                                             0.00%                                                                               46.47%               20 - 2                                                                             442.90                                                                             1.05 CH2O 50° C.                                                                      300.0                                                                              0.488             16.72%                                                                              58.42%                                                                             0.00%                                                                               58.42%               20 - 3                                                                             441.42        50° C.                                                                      1250.0                                                                             0.486             24.46%                                                                              85.47%                                                                             0.00%                                                                               85.47%               20 - 4                                                                             353.40        boil                                                                               boil                                                                               0.486             30.01%                                                                              86.19%                                                                             0.00%                                                                               86.19%               21 - 0                                                                             446.70                                                                             1.0NaH/1EDDA                                                                             65° C.                                                                      16.0                                                                               0.491             7.03%                                                                               24.60%                                                                             0.00%                                                                               24.60%               21 - 1                                                                             444.89                                                                             65° C.                                                                            65° C.                                                                      85.0                                                                               0.489             17.26%                                                                              60.40%                                                                             0.00%                                                                               60.40%               21 - 2                                                                             443.09                                                                             1.05 CH2O 65° C.                                                                      175.0                                                                              0.487             22.05%                                                                              77.16%                                                                             0.00%                                                                               77.16%               21 - 3                                                                             441.24        65° C.                                                                      253.0                                                                              0.485             23.83%                                                                              83.38%                                                                             0.00%                                                                               83.38%               21 - 4                                                                             439.56        65° C.                                                                      1240.0                                                                             0.483             42.40%                                                                              85.38%                                                                             0.00%                                                                               85.38%               21 - 5                                                                             380.00        boil                                                                               boil                                                                               0.483             24.96%                                                                              75.50%                                                                             0.00%                                                                               75.50%               22 - 0                                                                             446.70                                                                             1.8NaH/1EDDA                                                                             65° C.                                                                      25.0                                                                               0.491             9.99%                                                                               34.96%                                                                             0.00%                                                                               34.96%               22 - 1                                                                             444.33                                                                             65° C.                                                                            65° C.                                                                      110.0                                                                              0.488             19.71%                                                                              68.97%                                                                             0.00%                                                                               68.97%               22 - 2                                                                             442.74                                                                             1.00 CH2O 65° C.                                                                      165.0                                                                              0.487             21.34%                                                                              74.67%                                                                             0.00%                                                                               74.67%               22 - 3                                                                             441.04        65° C.                                                                      208.0                                                                              0.485             21.40%                                                                              74.88%                                                                             0.00%                                                                               74.88%               22 - 4                                                                             439.65        65° C.                                                                      1292.0                                                                             0.483             23.72%                                                                              83.00%                                                                             0.00%                                                                               83.00%               22 - 5                                                                             394.70        boil                                                                               boil                                                                               0.483             25.87%                                                                              81.27%                                                                             0.00%                                                                               81.27%               23 - 0                                                                             450.70                                                                             1.9NaH/1EDDA                                                                             65° C.                                                                      33.0                                                                               0.491             11.14%                                                                              39.33%                                                                             0.00%                                                                               39.33%               23 - 1                                                                             448.95                                                                             65°  C.                                                                           65° C.                                                                      92.0                                                                               0.489             18.65%                                                                              65.84%                                                                             0.00%                                                                               65.84%               23 - 2                                                                             447.21                                                                             1.05 CH2O 65° C.                                                                      148.0                                                                              0.487             21.69%                                                                              76.58%                                                                             0.00%                                                                               76.58%               23 - 3                                                                             445.41        65° C.                                                                      230.0                                                                              0.485             23.32%                                                                              82.33%                                                                             0.00%                                                                               82.33%               23 - 4                                                                             443.77        65° C.                                                                      1276.0                                                                             0.483             24.79%                                                                              87.52%                                                                             0.00%                                                                               87.52%               23 - 5                                                                             408.62        boil                                                                               boil                                                                               0.483             26.43%                                                                              85.92%                                                                             0.00%                                                                               85.92%               __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________                                % 3KPNa2   moles after                                                                          % conversion                       Exp Temp °C.                                                                     M CH2O                                                                              EDDA:NaOH                                                                              final wt                                                                            recyclized                                                                           mole3KP                                                                             sampling                                                                             recyclized                         __________________________________________________________________________     1   50.00                                                                               1.05 1.90    373.40                                                                              31.39%                                                                               0.45 0.48  92.99%                             2   65.00                                                                               1.00 1.90    364.00                                                                              31.91%                                                                               0.45 0.49  91.91%                             3   75.00                                                                               1.05 1.90    376.40                                                                              29.53%                                                                               0.43 0.49  88.04%                             4   50.00                                                                               1.00 1.90    372.80                                                                              31.77%                                                                               0.46 0.49  93.37%                             5   50.00                                                                               1.00 1.80    370.30                                                                              32.10%                                                                               0.46 0.49  94.00%                             6   50.00                                                                               1.05 1.80    388.95                                                                              30.89%                                                                               0.46 0.49  94.41%                             7   65.00                                                                               1.05 1.80    393.60                                                                              29.71%                                                                               0.45 0.48  93.07%                             8   65.00                                                                               1.00 1.80    415.60                                                                              24.86%                                                                               0.43 0.48  88.82%                             9   65.00                                                                               1.05 1.90    417.70                                                                              29.82%                                                                               0.48 0.48  98.08%                             __________________________________________________________________________             % 3KPNA2                                                                              % difference                                                                          % unopened                                                                            % EDDANa3                                                                              % conversion                                                                          % total conv                       Exp     after stage 1                                                                         at 1 -recycle                                                                         eKPNa2 by litr to ED3ANa3                                                                            on ED3ANa3                         __________________________________________________________________________     1       89.48% -3.51% 2.05%  38.00%  91.28% 95.74%                             2       85.25% -6.86% 1.88%  38.32%  94.89% 98.23%                             3       85.19% -2.85% 2.09%  36.55%  93.40% 97.87%                             4       86.10% -7.27% 2.17%  38.16%  96.58% 100.87%                            5       86.28% -7.72% 2.28%  37.50%  94.27% 98.99%                             6       86.19% -8.22% 2.69%  35.39%  93.45% 99.10%                             7       85.38% -7.69% 2.85%  34.13%  91.20% 98.76%                             8       81.27% -7.55% 3.08%  32.54%  91.81% 100.56%                            9       85.92% -13.18%                                                                               2.43%  32.10%  91.03% 87.70%                             __________________________________________________________________________

The data demonstrate that both mass balances and conversions to product are excellent. ED3A was measured by copper(II) salt titration, and 3KP was measured by high pressure liquid chromatography (HPLC). The final column in the Table 1 shows the mass balances for stage 3 (the formation of 3KP) of the reaction. The 9th column in Table 2 shows the percent conversion to product based on recyclization. Recyclization was achieved by acidifying a sample of the reaction mass with HCl to a pH of 2.0. These samples were then allowed to stand in an oven at 40° C. overnight and then on a bench at room temperature for 2 days prior to analysis. This technique was employed to verify the titration results, ensuring that all product was recyclized to 3KPH₂. Mass balances are not as good as those that were titrated, and this may be attributed to HPLC error and dilution error, etc. 

What is claimed is:
 1. A process for the preparation of a compound represented by the following formula: ##STR5## wherein X and Y each represent hydrogen or an alkali metal or alkaline earth metal, comprising:a. reacting formaldehyde with an alkali metal or alkaline earth metal salt of ethylenediaminediacetic acid to form 1,3-bis(carboxymethyl)imidazolidine, and b. reacting the product of step a with a cyanide source wherein said process is carried out at a temperature of about 0° to 110° C.
 2. The process of claim 1, wherein the reaction of formaldehyde and ethylenediamine dialkali metal acetate is conducted at a temperature from about 0° to about 65° C.
 3. The process of claim 1, wherein the reaction of formaldehyde and ethylenediamine dialkali metal acetate is conducted at a temperature from about 15° to about 65° C.
 4. The process of claim 1, wherein the reaction of step b is conducted at a temperature from about 0° to about 65° C.
 5. The process of claim 1, wherein the reaction of step b is conducted at a temperature from about 15° to about 65° C.
 6. The process of claim 1, wherein said formaldehyde is used in a slight molar excess.
 7. The process of claim 1, wherein said cyanide source is used in a slight molar excess.
 8. The process of claim 1, wherein said cyanide source is selected from the group consisting of hydrogen cyanide and alkali metal cyanide. 